Talanta - Biblioteca UMA1196 C.B. Ojeda et al./ Talanta 42 (1995) 1195-1214 tion of delayed spectra. In this procedure, pro- duction of a derivative spectrum is achieved with the use

E L S E V I E R Talanta 42 (1995) 1195-1214

Talanta

Review

Recent developments in derivative ultraviolet/visible absorption spectrophotometery

C. Bosch Ojeda, F. Sanchez Rojas, J.M. Cano Pavon* Department of Analytical Chemistry, Faculty of Sciences, University of Mdlaga, 29071 Md/aga, Spain

Received 11 October 1994; accepted 10 March 1995

Abstract

The instrumental development and analytical applications of derivative ultraviolet/visible region absorption spectrophotometry produced in the last seven years (since 1987) are reviewed.

1. Introduction

In a review published some years ago [1] we exposed the theoretical aspects, instrumental devices and analytical applications of derivative ultraviolet/visible spectrophotometry (DS) until 1986. Although this technique does not really constitute a very important innovation, its ability to solve problems, especially for binary and ternary mixtures of compounds whose spectra show considerable overlapping, have made its use grow spectacularly over the last few years, especially in pharmaceutical, clinical and biochemical, as well as in inorganic and organic analysis.

The purpose of this paper is to review the publications on instrumental and theoretical aspects of derivative spectrometry and its use in the diverse fields of applications published since 1987, in order to fill the gap existing since the publication of our first review.

2. Theoretical and instrumental aspects

Over the last few years, the use of digital

* Corresponding author.

0039-9140/95/$29.00 © 1995 Elsevier Science B.V. All rights

differentiation by means of computers to ob- tain derivative spectra has been the usual procedure. Higher order derivatives can easily be obtained. General principles of these methods have been reviewed [2], and diverse interferences for coupling conventional spectrophotometers to microcalculations have been developed [3]; diverse algorithms (such as those of Fourier and Savitzky-Golay) are often used for obtaining the derivative spectra [4].

Diode-array spectrophotometers are actually widely used owing to their speed. Different computer-based data-acquisition systems for use with diode-array spectrophotometers have been described [5]. Diverse programs were developed to control the system and to process the results. Program functions usually included: (i) acquisition of data and correction for diode sensitivity, (ii) correction for positional shifts in array, (iii) creation of the data-base, (iv) fitting of the baseline, location of peaks, conversion to wavelength and identification of elements present, (v) display of raw and enhanced data from individual arrays, and (vi) use of an artifi- cial intelligence approach to identify components of a sample [6].

The attained derivative spectra have been assayed by other procedures, e.g. by subtrac-

reserved

1196 C.B. Ojeda et al./ Talanta 42 (1995) 1195-1214

tion of delayed spectra. In this procedure, pro- duction of a derivative spectrum is achieved with the use of a single data system without the creation of noise and without the need for computer software; the spectrum is stored in one half of the memory. A small horizontal shift is made, the size of which is not critical, and the resultant is transferred to the second half of the memory; the derivative spectrum is then created by subtraction of one half from the other [7].

An inconvenience of the derivative technique is that the signal-to-noise ratio (S/N) becomes progressively worse for higher orders. For this reason, practical derivative techniques include some degree of low-pass filtering or smoothing to control the increase in noise. Over the last few years, this problem has usually been solved by three types of digital filtering: ensemble averaging, least-squares polynomial smoothing and Fourier smoothing. Several computer programs were written for the actual applications of the concepts of these digital filters on UV/ visible spectrophotometer systems; as a result, ensemble averaging could not be applied as a routine operation for the spectrophotometer used; the maxima S/N enhancement factors achieved by least-squares polynomial smoothing were 6.17 and 7.47 for the spectra of Gaus- sian and Lorentzian distribution models, and 16.42 and 11.78 by Fourier smoothing for the spectra of the two models, respectively [8]. Talsky concludes that, in general, the more favourable S/N was obtained from four to six orders of derivative when electronic differentiation combined with diverse filtering systems was used [9].

The precision and accuracy in derivative spectrophotometry have been evaluated in a wide variety of situations. Using a computerized numerical method, it has been concluded [10] that if the spectrophotometric measurements are accurate to four significant figures, the relative error of the first numerical derivative is 0.6%; if measurements are accurate to three significant figures, the relative error of the first numerical derivative is 6°/'0. Compared with conventional spectrophotometry, the first derivative from a recording spectrophotometer caused an average error of ~ 4%, but at the peak of the first derivative the error was ~ 2%. Kimbrell et al. [11] recently developed a theoretical study on the multiple interacting factors which determine precision in derivative spectrometry. According to this work, the precision

varies by close to an order of magnitude when reasonable combinations of factors levels are used; the derivative order typically interacts strongly with the polynomial degree of the smoothing and derivatizing functions, and with the window width of these functions.

Enhancement of the precision and accuracy in derivative spectrophotometry of highly ab- sorbing samples has been investigated using transmittance-ratio methods [12]. The precision and accuracy obtained in multi-component determinations have also been considered, especially in mixtures of pharmaceuticals [13,14]. Detection limits have been evaluated for different substances using diverse derivative orders [15]; in general, no appreciable differences from conventional photometry are observed.

2.1. Multicomponent analysis

Derivative UV/visible spectrophometry has been widely used over the last few years in the analysis of multicomponent mixtures. For this reason, diverse procedures for the resolution of overlapped derivative peaks have been applied. Thus, the zero-crossing method has been used for the first- and second-derivative spectra in diverse mixtures [16]. Another procedure used is the named "K-ratio" method, in which the K-coefficient dual wavelength spectrophotometric method is taken as the mathematical model in order to resolve the difference nth-derivative spectral data at one wavelength for determining diverse two-component systems with zeroth- derivative and n th-derivative spectra that were seriously interfered with [17,18].

Diverse computer programs have been applied to the analysis of multicomponents using derivative spectra. Delaye et al. [19] developed a program (DESpl) for the computerized recog- nition of the spectral components in known binary mixtures, whereas Park et al. [20] describe another program (SPECMAN PLUS), written in Pascal, which provides automated spectral comparison techniques, utilizing the value of the root-mean square (RMS) of each difference; this comparison routine of the program can deal with spectra of compounds of different concentrations and different spectral recording resolutions. Recently, a multivariate statistical tool, the partial least-squares (PLS) method, has been applied to derivative data with good results [21]; the PLS technique has a calibration step where the relationship is esti- mated from a set of reference samples, and this

C.B. Ojeda et al. / Talanta 42 (1995) 1195-1214 1197

step is followed by prediction in which the results of the calibration are iised to prediei or estimate the component concentration from the unknown sample spectrum.

Other procedures for multicomponent analysis using computer calculations have also been reported. The FDAS-SL method [22], which is a means of measuring the shift-length (SL, nm) of the maximum absorption wavelength of a compound by utilizing the first-derivative absorption spectrum (FDAS), was used in the simultaneous determination of binary mixtures; this method utilizes the shift of the absorption spectrum of a compound at surfactant concentrations above the critical micelle concentration and the mixed molar ratio is obtained from the shift-length; each concentration of the compound is calculated by Beer's law. Karstang and Kvaleim [23] describe a technique based upon regression modelling of spectra for accurate estimation of the concentration of analytes in the presence of background constituents; this novel technique gives reliable predictions, while all the contaminated samples are detected as outliers in the conventional approach.

2.2. Combination of DS with flow injection, liquid chromatography and kinetic analysis

The advent of a multi-dimensional detection system and the affordability of personal computers provided with software that allows stor- age and subsequent processing of data has fostered developments of new experimental procedures in which DS is used in combination with dynamic techniques, such as flow-injection and liquid chromatography.

The simultaneous determination of compounds in two-, three- and four-component mixtures with completely overlapping spectra was achieved by flow-injection with a diode-array detection system, using the third-derivative spectra in the range 214-290nm. The ab- sorbance spectrum of each solution was recorded 10.7 s after sample injection with an integration time of 0.4 s [24].

In liquid chromatography, the information supplied by derivative spectroscopy used as a detection system has been exploited in three different ways, namely: (i) using the first derivative of the elution profile obtained at the wavelength of the absorption maximum; in the- ory, the derivative should be zero at this point and therefore the disappearance of the main peak reveals the presence of other constituents

with different absorption features: this proce- diii'e:is ealied the "null spectral derivative technique"; (ii) using the complete derivative obtained by recording the elution profile; this procedure is known as the "spectral derivative mapping technique" [25,26]; (iii) using the derivative spectra of the components obtained around the maxima signal of the overlapped chromatographic peaks; the detector was set to collect a spectrum every 1 s, over an adequate wavelength range; this procedure makes possible the easy transformation of a chromatographic problem in a spectrophotometric problem [27].

Derivative techniques have also been used in kinetic analysis. A selective empirical data processing method based on a modification of the conventional kinetic derivative method has been reported [28]. The method is based on parameters not directly correlated with the ini- tial rate, but which are similar to those used in derivative spectrometry as the distance between two peaks or the value of the derivative at a single time. Two types of kinetic curves were tested, namely curves with and without induc- tion periods. Different-order derivatives were obtained by numerical differentiation using the Savitzky-Golay method. The proposed method is shown to provide improved selectiv- ity.

3. Applications

3. I. Inorganic analysis

The use of DS in inorganic analysis, especially in the determination of mixtures of metal ions, has undergone an appreciable increase in the last few years. Diverse chromogenic reagents (EDTA, dithizone, 8-hydroxyquinoline, some hydrazones, etc.) have been proposed. The different determinations achieved are described in Table 1. However, the analysis of anions has hardly been investigated; only the simultaneous determination of nitrite and nitrate in water using linear regression DS has been described [76].

3.2. Organic compounds

Binary and ternary mixtures of organic compounds have been widely analyzed using DS. Although pharmaceutical formulations are the mixtures most frequently assayed, and are es-

1198 C.B. Ojeda el aL / Talanta 42 (1995) 1195-1214

Table I Determination of metal ions

Elements Reagents Remarks Ref.

AI, Fe(Ill), Cu, 8-Hydroxyquinoline 1st deriv., extraction into 28 Ti, Ni chloroform~ binary, ternary

Be

Be, AI

Co

Co, Fe(ll)

Co, Cu

Cu, Fe(llI)

Cu, Ni

Cu, Ni

Cu, Zn

Cu, Zn, Mn(ll)

Fe(llI)

Fail)

Fe(lll), Bi

Hg

Hg, Co

Ir, Rh, Pt, Ag

La, Pr, Nd, Sin, Eu, Ho, Er

Mn

Mo

Mo, Ti

Beryllon III

5,8-Dihydroxy-l, 4- naphthoquinone

8-Hydroxyquinoline

3-(4-Phenyl-2-pyridinyl)- 1,2,4-triazine

Methylenediamine tetraacetic acid 2,(5-Bromo-2-pyridylazo)- 5-diethylaminophenol

Sodium cyanide

5,10,15,20-Tetrakis-(4- trimethylammonio-oheny I )porphine

2-(5-Bromo-2-pyridylazo)- 5-diethylaminophenol

EDTA

1,10-Phenanthroline

EDTA

Iodide + Pyronine G

Benzyl-2-pyridylketone-2- quinolylhydrnzone

Sulfochlorophenoazo- rhodanine

Triethylenetetramine- hexaacetic acid (TTHA)

(NH4)2S20$ + AgO)

and quaternary mixtures were analyzed

3rd deriv.

Simultaneous determination; 7.2-396 and 10.8-1080 ng ml - J, respectively

Ist deriv., cobalt is oxidized by air only in the presence of Fe(Iil) or V(V), extraction into chloroform is used

1st deriv., simult, determ., extraction into dichloroethane, 57-2000 and 2-200 ng ml-I , respectively

1st deriv., simult, determ.

Simult. determ., 2-10 lag ml- i of each ion

3rd deriv., simult, determ., 0.55-5.8 and 0.55-6.8 lagml - t , respectively

1st deriv., aqueous solutions of both metal ions were analyzed

4th deriv., determinations were performed in the presence of sodium dodecylsulphate

I st and 2nd deriv., simult. determ., using the equation set of solutions and the least- squares method

1st and 2nd deriv.

2nd deriv., 1-12 lag ml -I , iron is determined in bronze

1st deriv, 0.5-8.0 and 0.1- 35.7 lag ml- t, respectively

3rd deriv., 0.04-0.8 lag rol-

l st deriv., simult, determ.

Bromopyrogallol red

Salicylfluorone + hexadecylmethylammonium bromide

3rd deriv.

I st deriv., manganese is oxidized to permanganate

3rd deriv., simultaneous determ.

3rd deriv., simult, determ.

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48


Table I (continued)


Nd Tiron

Nd Ascorbic acid

Nd, Er 5,7-Dibromoquinolin-8-ol

Nd, Er 5-Suifo-7-iodoquinolin-8-ol (ferron) + diethylamine

Nd, Er 4-Benzoyl-3-methyl- l- phenylpyrazolin-5-one

Nd, Er

Nd, Sm, Eu, Gd, Tb, Dy

Ni, Co

Ni, Co

Ni, Cu, V

Ni, Cu, Zn

Ni, Cu, Zu

Pb

Pd, Pt

Pd, Pt

Pd, Nd, Sm, Eu, Ho, Er

Pr, Nd, Eu, Ho, Er, Tm

Pr, Nd, Dy

Sin, Gd, Dy, Nd

Ta

8-Hydroxyquinoline + diethylamine

HCI

2-(4,5-Dimethy l-2- thiozolylazo)-5- dimethylaminobenzoic acid

Benzyl-2-pyridylketone-2- quinolyihydrazone

2-(5-Bromo-2-pyridylazo- 5-diethylamino)phenol

4-(2-Pyridylazo)resorcinol

I -(2-Pyridylazo)-2-naphthol

1,10-Phenanthroline + Rose Bengal

Dithizone

N,N-Diethyl-4- nitrosoaniline

EDTA and oxalic acid

2-Thenoyltrifluoroacetone and 2,6-dimethylpyridine

5-Bromo-2-(2-pyridylazo)- 5-diethylaminophenol

3rd deriv. 49

5th deriv., Nd is determined in 50 magnesium alloys

3rd deriv., simult, determ., 51 Trition X-100 is used as suffactant, up to 18 lagml -~ of Nd and up to 21 lagml -~ of Er

3rd deriv., up to 14lagml - t for 52 Nd and up to 13 lagml -~ for Er

3rd deriv., simult, determ., 53 5.8-29 and 6.7-40 lag ml -L respectively

3rd deriv., 3-18 and 4.5-21 lag ml - ~, respectively

1st deriv.

ist deriv., simult, determ., the method makes possible the determination of both elements in nickel minerals

1st deriv., 480 and 512 nm, 57 simult, determ.

1st deriv., simult, determ., 58 these elements have been determined in petroleum samples

Ist deriv., simult, determ., 59 Kalman filter is used

2nd deriv., simult, determ., 60 0.3-2.0, 0.5-3.0 and 0.5-3.0 lag ml - t, respectively

4th deriv., extraction of the 61 complex into chloroform

5th deriv., simuit, determ., 62 extraction into carbon tetrachloride

1st deriv., simult, determ., 63 567.5 and 549.2 nm, respectively

2nd and 4th deriv., Sm and Eu 64 can be determined in the presence of other metals

2nd deriv.

2nd deriv., spectra in acid solutions were measured

2nd deriv., 4th deriv., spectra in acid solutions (HCIO4) were measured

Ist deriv., Ta is determined in nickel-based alloys containing niobium

54

55

56

65

66

67

68

1200

Table 1 (continued)

C.B. Ojeda et al. / Talanta 42 (1995) 1195-1214


Ti Hydrogen peroxide 2nd deriv., up to 10 lag ml-~, Ti 69 is determined in steels

U, Th Carminic acid Ist deriv., simult, determ., 2- 70 50 and 1-40 lag ml- i respectively

U, Th 4-(2'-Thiazolylazo) 1st deriv., simult, determ. 71 resacetophenone oxime

V, Co 4-(I'H-I', 2',4'-Triazol-3'- 2nd deriv., simult, determ., 72 ylazo)-2-methylresorcinol 0. I 0- 1.02 and 0.12- I. ! 8

lag ml- ~, respectively

w, Mo Sacilylfluorone and 73 cetyltrimethylammonium bromide

Zn meso-Tetrakis 2nd deriv., up to 0.24 lag ml- ~, (3,5, dibromo--4- zinc can be determined in hydroxyphenyl)porphyrin biological samples (T(DBHP)P)

74, 75

pecially considered in the next paragraph, other diverse mixtures (antioxidants, pesticides, herbicides, etc.) have been determined with good results. Table 2 shows the diverse procedures described since 1987. Li and Shi [100] reviewed years ago the articles published on organic compounds (including pharmaceuticals and clinical samples) until 1988.

3.3. Pharmaceutical analysis

The application of DS in pharmaceutical analysis has undergone explosive growth over the last 5 years. This fact is due to the easy application of this technique to pharmaceutical formulations, which are usually mixtures of two or three components of different chemical structures, and therefore show UV/visible spectra with different peaks and/or different ampli- tudes. DS has also proved particularly useful in eliminating matrix interferences, including those of aromatics, which have weak absorption in the near ultraviolet.

More than a hundred methods for pharmaceutical mixtures have been described over the last few years [101-215], and are shown in Table 3. Particularly numerous are the determinations referring to mixtures of antidepressives and transquilizers, as well as to formulations containing caffeine with other stimulants and antihystaminics, or mixtures of diverse sui- phamides or antibiotics.

3.4. Analysis o f amino acids, proteins and other biological compounds

DS has been widely used in the analysis of binary and ternary mixtures of amino acids. Mixtures of phenylalanine, tyrosine and triptophane have been especially studied. Proce- dures described since 1987 [216-235] are shown in Table 4.

3.5. Clinical and forensic analysis

DS has been proposed for the identification of compounds in mixtures of special interest in clinical and forensic analysis, and diverse general reports have been published in recent years [236,237]. Specific procedures are summarized [238-257] in Table 5. Diverse procedures using second derivative spectra have been described for the determination of haemoglobin and carboxyhaemoglobin in blood, as well as for the analysis of diverse pharmaceutical compounds in biological fluids.

3.6. Food analysis

Procedures involving the application of UV/ visible DS to food analysis are summarized [258-271] in Table 6. In general, derivative technique has been especially used in the determination of additives (colouring, flavour enhancers) in foods.


Table 2 Determination of organic compounds

Compounds Remarks Ref.

Alkaloids Total alkaloids of Coptis chinensis were 77 extracted in HC1-MeOH and determined

3rd and 4th deriv, was used 78 Antioxidants (butylated hydroxyanisole, butylated hydroxytoluene and Pr gallate)

Carbaryl and chlorpyrifos

Carbendazim

Chlorophenols

Chlorpromazine and fl- cyclodextrin

Cocaine

2-Fuffuraldehyde, 5- hydroxymethyl fuffuraldehyde and malonaldehyde

5-Hydroxyflavonoids

Indulin C

1 ndazole- 3-carboxylic acid

Nicotine

Paeonol

Phenol compounds

Phloroglucinols

Piperonyl butoxide, neopynamine, permethrin and fenitrothion

Polymers

Polymers

Salieylaldeh~le arid para -hydroxybenzaldehyde

PLS was also applied to simultaneous determination

2nd deriv., the compound is determined in Kolfugo extra formulations

Ist deriv., two-, three- and four-component mixtures were possible using multivariate calibration

2nd deriv., the binding constant between both compounds in aqueous solution was determined by means of an iterative calculation method

Ist and 2nd deriv., the compound (up to 10 lag ml-~) is determined in methanol

Simult. determ., the three chemicals were reacted previously with 2-thiobarbituric acid, PLS analysis is used

I st deriv.

2nd deriv., spectra are used for studies of degradation of lignin

2nd, 3rd and 4th deriv., several isomers N2 and N 2 substituted were identified using this technique

Ist and 2nd deriv., nicotine is determined in tobacco products

1st deriv., the derivative values at 279 and 242 nm were used for quantification of paeonol, and their difference was proportional to up to 10 lag ml - ~ of this substance

Ist and 2nd deriv., mixture of to up to nine phenols (phenol and halogen, nitro-, methoxy- and methyl-derivatives, 1-100 laM) were determined with use of the mathematical algorithm MULTI3

2nd deriv., flow-injection analysis coupled with liquid chromatography and a diode array detector was used

2nd deriv., binary mixtures can be resolved

1st and 4th deriv., polystyrene and mixtures of several prepolymers were studied

2nd deriv.

2nd deriv., simult, determ.

79

80

81, 82

83

84

85

86

87

88

89

90

91

92

93

94

95

96

1202

Table 2 (continued)

C.8. Ojeda et aL / Talanta 42 (1995) 1195-1214


Salicylaldehyde, 3- 1st deriv., simult, determ. 97 hydroxybenzaldehyde and 4-hydroxybenzaldehyde

Tocopherols

Trifluralin, benfluralin, isopropalin and oryzalin (herbicides)

2nd deriv., individual ~-, p-, 7- and ~- tocopherols were determined

1st deriv., detection range found was 1-7 pg ml-

98

99

Table 3 Methods described for the analysis of compounds in pharmaceutical formulations


Acetylsalicylic acid and 4th deriv., 0.02-0.2mgml - I for each 101 chlormezanone compound

Acetylsalicylic acid and 276, 286, 304 and 314 nm for acetylsalicylic 102 paracetamol acid; 256 and 320 nm for paracetamol.

Regression equations must be used

2nd and 3rd deriv., 4-(6-methylnaphthalen-2- yl)4-oxobut-2-enoic acid is used as reagent

Aliphatic thiol drugs 103

Acetaminophen and Binary mixtures only 104 orphenedrine, ibuprofen or chlorzoxazone

Aminazine and diprazine 250-255 nm 105

4-Aminophenol 2nd deriv., 224 nm, 0.5-38% of 4- 106 aminophenol can be determined in the presence of paracetamol

I st and 2nd deriv. Aminodarone hydrochloride

Amitriptyline and chlordiazepoxide or perphenazine

Amoxycillin

Amoxycillin and cephalexin

! st deriv.

107

108

2nd deriv., 280 nm, 3.3-55.4 pg ml-

2nd deriv., up to 90 lag ml- i for amoxycillin (276 nm) and up to 60 lag ml- t for cephalexin (267.5 nm)

Ascorbic acid and analgin 1st deriv. I l l

Asparaginase 259 nm, 0.05-0.125 mg ml - i I 12

Benzalkonium HCI 2nd deriv., 255-275 nm, determination can be 113 achieved in the presence of pilocarpine, hypromellose and polivinyl alcohol

Benzodiazepines 1st and 2nd deriv., single compounds only 114

Benzodiazepines and/or 2rid deriv., 19 compounds can be clearly 115 their metabolites identified, whereas four can only be differentiated

two by two (diazepam-prazepam and alprazolam-cstazolam)

Benzodiazepines and Determination in biological fluids 116 benzophenones

109

II0


Table 3 (continued)


Bretylium tosylate, 1st deriv., picric acid is used as reagent, 5-20 117 hyoscine Bu bromide, lag ml-~ for each compound oxyphenonium bromide, cetrimide and benzalkonium chloride

Bromazepam I t 8

Bufotoxin lactone 119

2nd deriv., 237-247 nm, up to 30 lag ml-

2nd deriv., 359 and 376 nm, determination is made in Houzhenwan (traditional chinese antipyretic)

Caffeine and amidopyrine 1st deriv., 275-296 nm, linear regression 120 method of multiwavelength is used

Caffeine and ist deriv. 121 antihistaminics

Caffeine and sodium 9-33 lag ml-1(269 nm) for caffeine and 6.5-19.5 122 benzoate (241 nm) for sodium benzoate

Canrenone 2nd deriv., 300 nm, 2-10 lag ml-~, 123 determination in the presence of spironolactone

Carbimazole and 3rd deriv., 265 and 295 nm, respectively 124 methimazole

Cephalosporins and their 2nd deriv., 4-24 lag ml-~ 125 degradation products

Clomiphene citrate and 1st deriv. 126 tamoxifen citrate

Chlorpheniramine maleate 2nd deriv., 228-260 nm, 4-36 lag ml-~ 127

Chlorpheniramine maleate 128 and phenylephrine- HCI

Chlorphenoxamine and 225, 232 nm for chlorphenoxamine and 256, 129 caffeine 283 nm for caffeine

Chlorpromazine and its 3rd deriv. 130 sulphoxide

Clotrimazole 1st deriv., 266 nm 131

Captotril and 1st deriv., 228-248 nm 132 hydrochlorothiazide

Cytarabine and acyclovir 1st and 2nd deriv., 268 and 272, respectively 133

Danthron and phanquone I st deriv., previous formation of complexes 134 with metal ions

Diazepam and oxazepam 4th deriv. 135

Diazepam and otilonium Ist deriv., 264 and 406-408 nm, respectively 136 bromide

Dicloxacillin and ampicillin 2nd deriv., up to 60 lag ml - L for each compound 137

2,6-Diisopropylphenol 2nd deriv., 0.10-0.25 lag ml-~ 138

Diphenhydramine or 2nd deriv., extraction into chloroform 139 naphazoline, and methylene blue

Diphenhydramine

Diphenhydramine, ephedrine and pentoxyverine

2nd deriv., 215 or 251 nm 140

Ist and 4th deriv. 141

1204 C.B. Ojeda et al. / Talanta 42 (1995) 1195-1214

Table 3 (continued)


Diloxanide furoate and I st and 2nd deriv., 0.02-0.1 mg ml- t (262 nm) 142 metronidazole and 0.04-0.2 mg ml - ~ (248 nm), respectively

Domperidone 1st deriv. 143

Enalapril maleate 144

Estradiol and progesterone 145 or testosterone

Estrone, equilin, 17-~- 146 estradiol and 17-~- dihydroequilin

Ethinyl oestradiol and 147 norethisterone

Famotidine 148

Febuprol 149

Fendiline HCI and other 150 related compounds

Glibenclamide, mebeverine 151 and clopamide

Hydrochlorothiazide and 152 amiloride HCI

Hydrocortisone, 153 dexamethasone, prednisolone and prednisone

4-Hydroxyphenoxymethyl 154 penicillin

Imipramine and 155 amitriptyline

imipramine, trimipramine, 156 amitriptyline, dothiepin and cyproheptadine

Insulin 157

lsoniazid and pyridoxine or thiacetazone

fl-Lactam antibiotics

Levamisole hydrochloride

Levodopa

Levodopa

Lidocaine

Methylene blue, hexamethytene tetramine and resorcinol

Minoxidil and retinoic acid

Nifedipine

Nitofurantoin and phenazopyridine

Notriptyline and perphenazine

4th deriv.

I st, 2nd, 3rd and 4th deriv., 280 and 338 nm

1st and 2nd deriv.

2nd deriv., 304 nm

276 and 280 nm

2nd deriv., 0.25-1 g I -

2nd deriv., determination can be achieved in the presence of their degradation products

Ist deriv., 284.7 nm

1st deriv.

4th deriv., 304-314 nm, 0.06-0.30 mg ml - i

Ist and 2nd deriv., 0.62-10.14 pgml - I and 0.63-10.40 pg ml - t , respectively

I st and 2nd deriv.

7th deriv., bovine and porcine insulin can be discriminated

Ist deriv., 8.2-41.1 pgml -~ and 7.1-23.6pgml -~

Determination in turbid solutions containing liposomes

Ist deriv., 239 nm

2nd deriv., 267 nm

2nd deriv., 280-290 nm, 2.4-120 lag ml -

3rd deriv.

Ist deriv., 273, 221 and 300 nm, respectively

Ist deriv., 290 and 351 nm, respectively

I st deriv., 402 nm

Ist deriv., 335 and 317 nm, respectively

4th deriv., 239.6 and 268.8 nm, respectively

158

159

160

161

162

163

164

165

166

167

168

C.B. Ojeda et al./ Talanta 42 (1995) 1195-1214 1205

Table 3 (continued)


Oestradiol 3 -12 lag m l - ~ 1 6 9

Oxytetracycline 170

Parabens 171

Paracetamol 2nd deriv. 172

Paracetamol and 2nd deriv., 270.8 and 278,9 nm, respectively 173 chlorzoxazone

Paracetamol and 2nd deriv., 250.2 and 227,6 nm, respectively 174 methocarbamol

Paracetamol and 1st deriv., 256.7 and 242.8 nm, respectively 175 phenylpropanolamine HCI

Penicillins and 1st, 2nd and 3rd deriv., 13 penicillins and five 176 cephalosporins cephalosphorins in different combinations

were assayed

Perphenazine and I st and 2nd deriv., 1 - 8 lag m l - ~ and I - 30 lag m l - ~, 177 amitriptyline respectively

Perphenazine and 1st and 2nd deriv., other tranquilizers and 178 amitriptyline antidepressants were also assayed

Phenothiazines 1st and 2nd deriv. 179

Phenothiazines 2nd and 4th deriv. 180 Phenothiazines 2nd deriv., binary mixtures 181

Phenylephrine I st deriv., determination is in the 182 presence of chlorapheramine, sulphacetamide or prednisolone

l-Phenylethylamine Determination is in the presence of 183 fosfomycin

Phenylephrine HCI and 1st deriv., 275 and 237 nm, respectively; 184 carbinoxamine maleate related compounds were also assayed

Phenytoin and 2nd deriv. 185 phenobarbital

Phenytoin 2nd deriv., 4 .5-160 lamol 1 - t 186

Prazosin and polythiazide 2nd deriv., 346 and 236 nm. respectively 187

Prenylamine lactate and 2nd deriv. 188 other related compounds

Propofol 2nd deriv., 286 rim, 0.1-0.25 mg m l - ~ 189

Pseudoephedrine and Ist deriv. 190 chlorpheniramine

Pseudoephedrine, 2nd deriv., 240-300 nm 191 chlorpheniramine and dextromethorphan

Puerarin I st deriv., 3 .2-16 lag m l - ~ 192

Rifamixin 2nd deriv. 2 -40 lag ml-~ 193

Salbutamol Ist deriv., 286 nm 194

Salbutamol 2nd and 4th order, 1-80 lag mt -~, determination 195 is in the presence of gelatine

Salicylic and salicyluric Ist deriv., 2 .6-52 tag m l - i and 2.1-42 lag m l - t 196 acids

Simvastatin 197

1206

Table 3 (continued)

C.B. Ojeda et al. / Talanta 42 (1995) i!95-1214


Spironolactone and hydrochlorothiazide

Sulfamethoxazole and trimethroprim

Sulfacetamide, sulfadimidine and sulfathiourea

Sulfonamides

Sulphamethizole

Sulphaquinoxaline and pyrimethamine

Synephrine

Tetracyclines

Theophylline

Thiamine, riboflavine, nicotinamide, pyridoxine and ascorbic acid

Thiamine, riboflavine, nicotinamide, pyridoxine and calcium pantothenate

Thiobarbituric acid

Thioxanthenes

Tocopherols

Tolazoline, atropine homatropine, tetrahydrozoline and xylometazoline

Triamterene and hydrochlorothiazide or xipamide

Triamphenicol glyeinate and N-acetylcisteine or 4- hydroxyisophthalic acid

Trimethroprim and sulfamethoxazole

198

280 and 290 nm, respectively 199

! st deriv. 200

1st and 4th deriv., Bratton-Marshall reaction combined with derivative photometry is used

Ist deriv., up to 43 ~gml -s, determination is in the presence of nitrofurantoine

ist deriv., 1-25 mg ml-a and 1-50 mg m l - I respectively

1st deriv.

2nd deriv.

I st deriv., 284, nm

Multiple linear regression analysis is used

1st deriv., multicomponent program is used

2nd deriv., determination is in the pressure of reactive products of lipid peroxidation in plants

Ist deriv., 4-40 I~g ml-

:-,/~-, 7- and 6-tocopherols were determined at 298, 302, 304 and 306 nm, respectively I st deriv., picric acid is used as reagent, extraction is made into chloroform

I st deriv.

2nd deriv., 274-278 nm, 6-55 lag ml-i for triamphenicol

201

202

203

204

205

206

207

208

209

210

211

212

213

214

215

3. 7. Environmental analysis

A few applications o f derivative UV spec- t ropho tomet ry to environmental analysis have been described over the last few years. High-order derivative absorpt ion spec t rophotomet ry has been used in the determinat ion o f oil in waste water to avoid complex sample extrac-

t ion and to eliminate interference by other chemical species; the calibration curve varied rectilinearly up to 100 mg 1- ~ o f oil, with 0.05 N H2SO4 as reference s tandard and light petroleum as blank [272].

Derivative spec t rophotomet ry has also been used in combina t ion with thermal soil desorp- t ion in the field screening o f b e n z e n e - t o l u e n e -

C.B. Ojeda et al./ Talanta 42 (/995) //95-1214 1207

Table 4 Methods for the analysis of amino acids and proteins


Adenine and thymine 2nd deriv., adenine and thymine were 216 determined in DNA (not more than 10 ~tg DNA is required)

Amino acids 2nd deriv., aromatic amino-acids were tested 217

Amino acids 2nd deriv, and size-exclusion HPLC were 218 combined and applied to the determination of aromatic amino acids of polypeptides

Chlorophylls a and b 1st deriv., 671 nm for a and 467 nm for b 219

Metaloporphyrins 3rd deriv., the method is based on 220 variation of the Soret band wavelength with the type of functional group structure of the 20-carbon porphyrin chromophore

Phenylalanine, tyrosine and Factorial analysis procedure for interpreting 221 triptophane derivative spectra is proposed; application is

made to the determination of these compounds in the presence of aromatic chromophores content in mitochondrial proteins

Ibidem 2nd deriv. 222

Ibidem Phenylalanine is determined in the presence 224 of the other compounds by means of the negative derivative peak near 258 nm

Phospholipids HPLC 2nd deriv, is used; 225

Phosphotyrosine

Polynucleotides

phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine and phosphatidic acid were characterized

HPLC 2nd deriv, is used, phosphatyrosine residues in peptides were identified

Conformational isomerizations of polynucleotides are studied by means of 4th deriv, spectrophotometry

HPLC deriv, spectrophotometry is used for the separation and detection of proteins and peptides

4th deriv, is used for protein quantification during purification

Size-exclusion HPLC derivative spectrophotometry is used

Detection of diverse proteins and phenol were achieved in DNA samples

2nd deriv., proteolysis of native bovine somatotropin is studied

2nd deriv., presence of tryptophan in peptides is studied

2nd deriv., both amino acids were determined in synthetic peptides

226

Proteins 229

Proteins 230

Proteins 231

Proteins and phenol

Somatotropin

Tryptophan

Tryptophan and tyrosine

227, 228

232

233

234

235

TAL 42:9-B


Table 5 Clinical and forensic analysis

Substances Type of Remarks Ref. sample

AIIopurinol and uric Urine Ist and 2nd deriv. (284 and 243 238 acid nm, respectively), 2-12 pg ml-

Bile salts 2nd deriv., critical micellar 239 concentrations of bile salts were determined

Cerebroespinald Ist and 2nd deriv., simultaneous 240 fluid determination, effects of turbidity

are minimized

Blood 2nd deriv., 418 nm 241

Blood Sorer region of the UV spectrum 242 is used, method has been applied in postmortem blood samples

Plasma 2nd deriv., 281 nm, I - 100 ~g ml-

Urine 3rd deriv., limit of detection is i 5 0 ng ml - i

Ist deriv.

Bilirrubin, methaemoglobin and oxyhaemoglobin

Carboxyhaemoglobin

Carboxyhaemoglobin

Ceftizoxime

Clonazepam

Haemoglobin

Haemoglobin (total) and carboxyhaemoglobin

Plasma or serum

Blood

Haemoglobin and Plasma urinary porphirins

Imipenem Plasma

Lipids Plasma

Lipids Plasma

243

244

245

246

Myoglobin

3rd deriv., carboxyhaemoglobin shows a maximum at 565 nm, and oxyhaemoglobin crosses the zero line at 565 nm

2nd deriv., limits of detection are 247 0.060 ttmol for haemoglobin and 10mmoll -~ for coproporphyrin and uroporphyrin

3rd deriv., 306-312 nm, 248 detection limit is 3 pg ml -

2nd deriv., lipid dienes as 249 markers of lipid peroxidation in heptane extracted from plasma from patients with arthritis are analyzed

Lipid peroxidation is used, and 250 hydroperoxidienes formed were studied by derivative spectrophotometry

2nd deriv., myogiobin is 251 determined in the presence of haemoglobin: diverse algorithms were used

Nitrazepam and Biological 5th deriv., limits of detection 252 clorazepam fluids are I I~g ml - ~ and 1.5 ~g ml - ~,

respectively

Paracetamol and Plasma 2nd deriv., recovery is slow 253 salicylate

Pesticides Serum and 2nd deriv., 245 nm, carbamate 254 gastric juice pesticides were analyzed,

detection limit for carbaryl is 250 ttg ml- i

Phenylbutazone and Plasma 4th deriv., 1-5 pg ml-~ for 255 oxyphenbutazone phenylbutazone and 3-8 gg ml-

for oxyphenbutazone

Porphyrins Urine 2nd deriv. 256

Rifampicin Plasma Binding of rifampicin by plasma 257 proteins is studied


Table 6 Food analysis

Substances Type of Remarks Ref. sample

:t- and fl-acids Hops

Chlorogenic acids Instant coffee

Enzymes Red fruited pears

Flavour enhancers Food preparations

Food colours Foods (synthetic)

Food colours Foods (synthetic)

2-Furfuraldehyde and 5- (hydroxymethyl)-2- furfuraldehyde

Lipid oxidation products

Pigments

Quinine

Refined oil

Saccharin, benzoic acid and ethyl-4- hydroxybenzoate

Orange juice

Vegetable oils

Orange-drink powder

Soft drinks

Virgin olive oils

Beverages

Seed oils Olive oils

Sorbic and benzoic Soft drinks acids

2nd deriv., simult. 258 determ.

2nd deriv., 325 nm, chicory 259 does not interfere

4th deriv., of peroxidase, esterase 260 and acid phosphatase were determined

1st and 2nd deriv., partial least- 261 squares and principal component regression modelling of spectrophotometric data have been used

2nd deriv., Amaranth, Tartrazide, 262 New Coceine, Sunset Yellow and Brillant Blue were determined in binary mixtures

I st deriv., Acid Blue, Food Red, 263 Acid Red and Food Yellow were determined simultaneously

1st deriv., thiobarbituric acid is 264 used as reagent, 436 and 414 nm were used

2nd deriv., degree of rancidity of 265 diverse vegetable oils (peanut, sunflower, corn, soybean, grape seed) was determined

1st deriv., carminic acid and 266 citron yellow were determined at 468 and 548 nm, respetively

4th deriv., limit of detection is 5 267 ng ml-

2rid deriv., interfering oxidizing 268 products were removed with alumina

2nd deriv., peanut, sunflower, corn, soybean, grapeseed oils were determined

2nd deriv., 1-7 lag ml - t

269

270

271

e thy lbenzene-xy lene in solids [273]. Ano the r method has been developed for the analysis of env i ronmenta l polycyclic a romat ic hydrocar- bons (PAHs) utilizing an algori thm in which the samples spectrum was used to bui ld a vector con ta in ing the second to fifth deriva-

tives; this was mult iply regressed against similar vectors con ta in ing the corresponding derivative of the uni t molar UV spectra of the target PAH; the PAHs selected in this step were used for a second mult iple regression filter, fitting all possible compounds into a

1210 C.B. Ojeda et aL / Talanta 42 (1995) 1195-1214

single Beer's law model; a third filter, based on sensitivity analysis, selected the significant components of the sample system [274].

Finally, a second-derivative UV spectrophotometry method is described for the determination of nitrate in soils; ammonium nitrite and urea may be determined in the same experi- ments [275].

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Talanta - Biblioteca UMA1196 C.B. Ojeda et al./ Talanta 42 (1995) 1195-1214 tion of delayed spectra. In this procedure, pro- duction of a derivative spectrum is achieved with the use